Thiazines and thiazoles as agents for protecting materials

ABSTRACT

The novel and known thiazines and thiazoles of the formula (I)  
                 
 
     in which  
     R 1 , R 2  and n are as defined in the description, are highly suitable for use as biocides for protecting industrial materials.

BACKGROUND

[0001] The present invention relates to novel thiazines and novelthiazoles, to processes for their preparation, to novel mixtures ofthiazines and/or thiazoles with other agents for protecting materialsand to the use of novel and known thiazines and novel and knownthiazoles as microbicides for protecting industrial materials.

[0002] Certain thiazines and thiazoles and processes for theirpreparation are already known from the literature (cf. R. E. Hackler etal., Synthetic Commun., 1975, 5, 143-146). It is furthermore known thatsome thiazines can be used as fungicides in agriculture and horticulture(cf. JP-A-2000-119263). U.S. Pat. No. 4,584,305 discloses that somethiazoles have nematicidal action.

[0003] However, these known thiazines and thiazoles have not beendescribed as agents for protecting materials.

[0004] Surprisingly, it has now been found that the novel and knownthiazines and thiazoles of the general formula (i) are particularlysuitable for protecting industrial materials against attack bymicroorganisms.

SUMMARY

[0005] The invention relates to a method comprising treating anindustrial material with a compound of the formula (I)

[0006] wherein R¹ represents hydrogen or in each case optionallysubstituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl,R² represents hydrogen, alkoxycarbonyl or alkylcarbonyl and n represents1 or 2, and thereby protecting the industrial material.

[0007] The invention also relates to a compound of the formula (I)

[0008] wherein

[0009] R¹ represents hydrogen or in each case optionally substitutedalkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl,

[0010] R² represents hydrogen, alkoxycarbonyl or alkylcarbonyl and

[0011] n represents 1 or 2,

[0012] except for

[0013] 2-(phenylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,

[0014]  CAS No. [73122-32-4]

[0015] 2-[(3-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0016]  CAS No. [73122-33-5]

[0017] 2-[(4-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0018]  CAS No. [10554-28-6]

[0019] 2-(methylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,

[0020]  CAS No. [58842-19-6]

[0021] 2-[(4-methoxyphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0022]  CAS No. [73122-49-3]

[0023] 2-[(4-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0024]  CAS No. [73122-44-8]

[0025] 2-(ethylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,

[0026]  Beilstein reference No. [4-27-00-01718]

[0027] 2-[(4-nitrophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0028]  CAS No. [73122-52-8]

[0029] 2-[(3,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0030]  CAS No. [73122-34-6]

[0031] 2-[(2-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0032]  CAS No. [55545-14-7]

[0033] 2-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-1-phenylethanone,

[0034]  CAS-No.[88636-60-6]

[0035]2-{[3-(trifluoromethyl)-1,2,4-thiadiazol-5-yl]sulfanyl}-5,6-dihydro-4H-1,3-thiazine,CAS No. [62655-49-6]

[0036] 2-[(2,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0037]  CAS No. [73122-35-7]

[0038] 2-[(4-bromophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0039]  CAS No. [73122-41-5]

[0040] 2-[(2,6-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0041]  CAS No. [73122-36-8]

[0042] 2-[(3,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0043]  CAS No. [73122-37-9]

[0044] 2-[(3-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0045]  CAS No. [73122-45-9]

[0046] 2-[(2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0047]  CAS No. [73122-46-0]

[0048] 4-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-N,N-dimethylaniline,

[0049]  CAS No. [73122-51-7]

[0050] 2-[(4-fluorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0051]  CAS No. [73122-42-6]

[0052] methyl 2-(methylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,

[0053]  CAS No. [117389-66-9]

[0054] methyl2-(4-chlorobenzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate, CASNo. [117389-75-0]

[0055] methyl 2-(benzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,

[0056]  CAS No. [117389-66-9]

[0057] 2-[(2-methyl-2-propenyl)sulfanyl]-4,5-dihydro-1,3-thiazole,

[0058]  CAS No. [56502-83-1]

[0059] 2-[benzylsulfanyl]-4,5-dihydro-1,3-thiazole,

[0060]  CAS No. [41834-62-2]

[0061] 2-[(2-methylpropyl)sulfanyl]-4,5-dihydro-1,3-thiazole,

[0062]  Beilstein reference No. [1099990]

[0063] 2-[allylsulfanyl]-4,5-dihydro-1,3-thiazole,

[0064]  CAS No. [3571-74-2]

[0065] 2-[4-nitrophenylsulfanyl]-4,5-dihydro-1,3-thiazole,

[0066]  CAS No. [103482-99-1]

[0067] 2-[4-methoxyphenylsulfanyl]-4,5-dihydro-1,3-thiazole,

[0068]  CAS No. [13094-98-9]

[0069] 2-[4-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,

[0070]  CAS No. [103482-92-4]

[0071] 2-[2-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,

[0072]  CAS No. [55545-15-8]

[0073] 2-[3-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,

[0074]  CAS No. [103482-93-5]

[0075] 2-(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)-1-phenylethanone,

[0076]  CAS No. [17385-78-3]

[0077] 2-[methylsulfanyl]-4,5-dihydro-1,3-thiazole,

[0078]  CAS No. [19975-56-5]

[0079]2-{[(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)methyl]sulfanyl}-4,5-dihydro-1,3-thiazole, CAS No. [89943-80-6]

[0080] 2-[phenylsulfanyl]-4,5-dihydro-1,3-thiazole,

[0081]  CAS No. [62652-38-4],

[0082] 2-[(4-tert-butylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0083]  CAS No. [73122-48-2]

[0084] 2-[(4-chloro-2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0085]  CAS No. [73122-47-1]

[0086] 2-[(pentachlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0087]  CAS No. [73122-40-4]

[0088] 2-[(2,4,6-trichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0089]  CAS No. [73122-39-1]

[0090] 2-[(2,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0091]  CAS No. [73122-38-0].

[0092] The invention also relates to a method for protecting anindustrial material against attack and/or destruction by anmicro-organisms, characterised in that at least one compound of theformula (I) comprising placing a compound of formula (I) on the organismor the habitat of the organism, and (b) allowing the compound of formula(I) to act on the micro-organism or its habitat.

[0093] The invention relates to a microbicidal composition forprotecting industrial material, comprising at least one compound of acompound of the formula (I)

[0094] wherein R¹ represents hydrogen or in each case optionallysubstituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl,R² represents hydrogen, alkoxycarbonyl or alkylcarbonyl and n represents1 or 2, and at least one solvent or diluent.

[0095] The invention also relates to an industrial material comprisingan industrial material with a compound of the formula (I)

[0096] wherein R¹ represents hydrogen or in each case optionallysubstituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl,

[0097] R² represents hydrogen, alkoxycarbonyl or alkylcarbonyl and nrepresents 1 or 2. These and other features, aspects, and advantages ofthe present invention will become better understood with reference tothe following description and appended claims.

DESCRIPTION

[0098] The present invention provides the use of novel and knowncompounds of the general formula (I)

[0099] in which

[0100] R¹ represents hydrogen or in each case optionally substitutedalkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl,

[0101] R² represents hydrogen, alkoxycarbonyl or alkylcarbonyl and

[0102] n represents 1 or 2, their metal salts and acid additioncompounds as biocides for protecting industrial materials.

[0103] For the purpose of the present invention, the alkyl radicalsmentioned are, including in the meaning of alkylcarbonyl, in each casestraight-chain or branched and unsubstituted or substituted and contain1 to 12 carbon atoms, in particular 1 to 8 carbon atoms. Preferred alkylradicals are methyl, ethyl, propyl, butyl and octyl. The alkenyl andalkinyl radicals mentioned are in each case straight-chain or branched,and unsubstituted or substituted and contain 2 to 6 carbon atoms, inparticular 2 to 4 carbon atoms. Preference is given to propenyl andbutinyl. Cycloalkyl generally represents an unsubstituted or substitutedcycloalkyl radical having 3 to 8 carbon atoms, in particular 3 to 6carbon atoms. Preference is given to cyclopropyl and cyclopentyl. Thealkoxy radicals mentioned in the meaning of alkoxycarbonyl are in eachcase straight-chain or branched and unsubstituted or substituted andcontain 1 to 6 carbon atoms, in particular 1 to 3 carbon atoms.Preference is given to methoxy and ethoxy. Aryl generally represents anunsubstituted or substituted 6- to 10-membered aromatic radical, inparticular phenyl. Halogen generally represents fluorine, chlorine,bromine or iodine, in particular fluorine, chlorine and bromine.Heterocyclyl generally represents a saturated mono- or polyunsaturatedor aromatic 5- to 7-membered ring, in particular 5- or 6-membered ring,having one or more identical or different heteroatoms, in particular 1to 4 heteroatoms and preferably 1 to 3 heteroatoms, from the groupconsisting of N, O and S, preferably N and S, optionally with a furtherfused-on carbocyclic ring, in particular a 6-membered carbocyclic ring,preferably a 6-membered aromatic ring.

[0104] The above-mentioned radicals are in each case optionally mono- topolysubstituted, in particular mono- to trisubstituted, preferably mono-or disubstituted, by identical or different substituents, possiblesubstituents being in each case: halogen, alkyl, cycloalkyl, haloalkyl,alkoxy, haloalkoxy, hydroxyl, nitro, nitrile, amino, dialkylamino,carbonyl, phenyl, phenoxy, sulfanylthiazolyl or sulfanylthiazinyl.

[0105] Preference is given to compounds of the formula (I) in which

[0106] R¹ represents hydrogen or represents C₁-C₁₂-alkyl which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of

[0107] C₁-C₆-alkoxy; C₁-C₆-alkoxycarbonyl; in each case optionallyhalogen- and/or C₁-C₆-alkoxy-substituted phenyl or phenylcarbonyl;C₁-C₆-alkylcarbonyl; optionally halogen-substitutedC₃-C₈-cycloalkylcarbonyl; 5- or 6-membered heterocyclylcarbonyl having 1to 3 heteroatoms from the group consisting of N, O and S;

[0108] 5- or 6-membered heterocyclylthio having 1 to 3 heteroatoms fromthe group consisting of N, O and S; or

[0109] represents C₂-C₆-alkenyl, C₂-C₆-alkinyl, C₃-C₈-cycloalkyl orrepresents phenyl which is optionally mono- or polysubstituted byidentical or different substituents from the group consisting ofhalogen, C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-haloalkyl,C₁-C₆-haloalkoxy, C₁-C₆-alkoxy, nitro, nitrile, hydroxyl, amino,phenoxy, phenyl and di-C₁-C₆-alkylamino, or

[0110] represents a 5- or 6-membered heterocycle having 1 to 3 identicalor different heteroatoms from the group consisting of O, S, N, whichheterocycle optionally contains a fused-on aromatic 6-membered ring,

[0111] R² represents hydrogen, C₁-C₆-alkoxycarbonyl orC₁-C₆-alkylcarbonyl, and

[0112] n represents 1 or 2.

[0113] Particular preference is given to compounds of the formula (I) inwhich

[0114] R¹ represents hydrogen or represents C₁-C₈-alkyl which isoptionally substituted by C₁-C₃-alkoxy; C₁-C₃-alkoxycarbonyl; in eachcase optionally chlorine- and/or methoxy-substituted phenyl orphenylcarbonyl; C₁-C₃-alkylcarbonyl; optionally chlorine-substitutedC₃-C₅-cycloalkylcarbonyl; 5- or 6-membered aromatic heterocyclylcarbonylhaving 1 or 2 heteroatoms from the group consisting of N and S; 5- or6-membered heterocyclylthio having 1 or 2 heteroatoms from the groupconsisting of N and S, or represents C₂-C₄-alkenyl, C₂-C₄-alkinyl,C₃-C₆-cycloalkyl or represents phenyl which is optionally mono- totrisubstituted by identical or different substituents from the groupconsisting of chlorine, bromine, fluorine, C₁-C₄-alkyl,C₃-C₆-cycloalkyl, C₁-C₃-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy,hydroxyl, nitro, nitrile, amino, phenoxy, phenyl or di-C₁-C₃-alkylamino,

[0115] or represents a 5- or 6-membered aromatic heterocycle having 1 or2 heteroatoms from the group consisting of N and S and optionally afused-on phenyl ring,

[0116] R² represents hydrogen, C₁-C₃-alkoxycarbonyl orC₁-C₃-alkylcarbonyl, and

[0117] n represents 1 or 2.

[0118] Very particular preference is given to compounds of the formula(I) in which

[0119] R¹ represents hydrogen or represents methyl which is optionallysubstituted by ethoxy, ethoxycarbonyl, phenylcarbonyl,methoxyphenylcarbonyl, chlorophenylcarbonyl, pyrrolylcarbonyl,thienylcarbonyl, chlorocyclopropylcarbonyl, thiazolylthio,thiazinylthio, or

[0120] represents ethyl, propyl, butyl, octyl, cyclopentyl, benzyl,chlorobenzyl, phenyl, chlorophenyl, methoxyphenyl, methylphenyl,nitrophenyl, dichlorophenyl, trichlorophenyl, fluorophenyl,difluorophenyl, trifluoromethoxyphenyl, trifluoromethylphenyl, thienyl,benzothienyl, bromophenyl, dibromophenyl, nitrilophenyl,dinitrilophenyl, hydroxyphenyl, benzothiazolyl,trifluoromethylthiazolyl, dimethylaminophenyl, phenoxy, phenyl,dimethylphenyl, dimethoxyphenyl, ethylphenyl, propylphenyl, butylphenyl,cyclopropylphenyl, chloromethylphenyl, dichloromethylphenyl,chloromethoxyphenyl, methoxymethylphenyl, methylpropene, allyl,(2-sulfanylthiazolyl)butine, (2-sulfanylthiazinyl)butine,

[0121] R² represents hydrogen or methoxycarbonyl and

[0122] n represents 1 or 2.

[0123] The compounds of the formula (I) having the above-mentionedgeneral and preferred meanings are novel, and also form part of thesubject-matter of the present invention, except for the compounds:

[0124] 2-(phenylsulfanyl)-5,6-dihydro-4H-1,3-thiazine

[0125]  CAS No. [73122-32-4]

[0126] 2-[(3-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0127]  CAS No. [73122-33-5]

[0128] 2-[(4-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0129]  CAS No. [10554-28-6]

[0130] 2-(methylsulfanyl)-5,6-dihydro-4H-1,3-thiazine

[0131]  CAS No. [58842-19-6]

[0132] 2-[(4-methoxyphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0133]  CAS No. [73122-49-3]

[0134] 2-[(4-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0135]  CAS No. [73122-44-8]

[0136] 2-(ethylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,

[0137] Beilstein reference No. [4-27-00-01718]

[0138] 2-[(4-nitrophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0139]  CAS No. [73122-52-8]

[0140] 2-[(3,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,

[0141]  CAS No.[73122-34-6]

[0142] 2-[(2-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0143]  CAS No. [55545-14-7]

[0144] 2-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-1-phenylethanone,

[0145]  CAS-No. [88636-60-6]

[0146]2-{[3-(trifluoromethyl)-1,2,4-thiadiazol-5-yl]sulfanyl}-5,6-dihydro-4H-1,3-thiazineCAS No. [62655-49-6]

[0147] 2-[(2,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0148]  CAS No. [73122-35-7]

[0149] 2-[(4-bromophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0150]  CAS No. [73122-41-5]

[0151] 2-[(2,6-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0152]  CAS No. [73122-36-8]

[0153] 2-[(3,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0154]  CAS No. [73122-37-9]

[0155] 2-[(3-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0156]  CAS No. [73122-45-9]

[0157] 2-[(2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0158]  CAS No. [73122-46-0]

[0159] 4-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-N,N-dimethylaniline,

[0160]  CAS No. [73122-51-7]

[0161] 2-[(4-fluorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0162]  CAS No. [73122-42-6]

[0163] methyl 2-(methylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate

[0164]  CAS No. [117389-66-9]

[0165] methyl2-(4-chlorobenzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate

[0166]  CAS No. [117389-75-0]

[0167] methyl 2-(benzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate

[0168]  CAS No. [117389-66-9]

[0169] 2-[(2-methyl-2-propenyl)sulfanyl]-4,5-dihydro-1,3-thiazole

[0170]  CAS No. [56502-83-1]

[0171] 2-[benzylsulfanyl]-4,5-dihydro-1,3-thiazole

[0172]  CAS No. [41834-62-2]

[0173] 2-[(2-methylpropyl)sulfanyl]-4,5-dihydro-1,3-thiazole

[0174]  Beilstein reference No. [1099990]

[0175] 2-[allylsulfanyl]-4,5-dihydro-1,3-thiazole

[0176]  CAS No. [3571-74-2]

[0177] 2-[4-nitrophenylsulfanyl]-4,5-dihydro-1,3-thiazole

[0178]  CAS No. [103482-99-1]

[0179] 2-[4-methoxyphenylsulfanyl]-4,5-dihydro-1,3-thiazole

[0180]  CAS No. [13094-98-9]

[0181] 2-[4-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole

[0182]  CAS No. [103482-92-4]

[0183] 2-[2-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole

[0184]  CAS No. [55545-15-8]

[0185] 2-[3-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole

[0186]  CAS No. [103482-93-5]

[0187] 2-(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)-1-phenylethanone

[0188]  CAS No. [17385-78-3]

[0189] 2-[methylsulfanyl]-4,5-dihydro-1,3-thiazole

[0190]  CAS No. [19975-56-5]

[0191]2-{[(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)methyl]sulfanyl}-4,5-dihydro-1,3-thiazole CAS No. [89943-80-6]

[0192] 2-[phenylsulfanyl]-4,5-dihydro-1,3-thiazole

[0193]  CAS No. [62652-38-4]

[0194] 2-[(4-tert-butylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0195]  CAS No. [73122-48-2]

[0196] 2-[(4-chloro-2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0197]  CAS No.[73122-47-1]

[0198] 2-[(pentachlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0199]  CAS No.[73122-40-4]

[0200] 2-[(2,4,6-trichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0201]  CAS No. [73122-39-1]

[0202] 2-[(2,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine

[0203]  CAS No. [73122-38-0].

[0204] The novel compounds of the formula (I) can be prepared byreacting mercaptans of the formula (II) or salts thereof

R¹—SH  (II)

[0205] in which

[0206] R¹ is as defined above,

[0207]  with compounds of the general formula (III)

[0208] in which

[0209] R² and n are as defined above and

[0210] X represents halogen or a leaving group,

[0211] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid binder.

[0212] Alternatively, the novel compounds of the formula (I) can beprepared by

[0213] a) reacting mercaptans of the formula (II) or salts thereof

R¹—SH  (II)

[0214]  in which

[0215] R¹ is as defined above,

[0216]  with isothiocyanates of the general formula (IV)

[0217]  in which

[0218] R² and n are as defined above and

[0219] X represents halogen or a leaving group,

[0220] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid binder; or by

[0221] b) diazotizing primary amines of the general formula (V)

R¹—NH₂  (V)

[0222]  in which

[0223] R¹ is as defined above,

[0224] with a diazotizing agent and reacting the products with compoundsof the general formula (VI) or salts thereof

[0225]  in which

[0226] R² and n are as defined above,

[0227] if appropriate in the presence of a diluent and if appropriate inthe presence of a catalyst, or by

[0228] c) reacting compounds of the general formula (VII)

R¹—X  (VII)

[0229]  in which

[0230] R¹ is as defined above and

[0231] X represents halogen or a leaving group,

[0232] with compounds of the general formula (VI) or salts thereof

[0233]  in which

[0234] R² and n are as defined above,

[0235] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid binder.

[0236] The salts can be prepared and reacted in situ or employedundiluted. Suitable for use as salts are in particular the alkali andalkaline earth metal salts, preferably the alkali salts and particularlypreferably the sodium and potassium salts. The salts are prepared bycustomary chemical methods.

[0237] The starting materials of the general formula (II) to (VII) arecommercially available, described in the literature or preparable bysimple chemical operations.

[0238] The compounds of the general formula (III) and (IV) can, ifappropriate, be generated in situ and reacted directly, or they can beemployed as pure substance.

[0239] Suitable diluents, which are added, if appropriate, are bothwater and all customary inert organic solvents. These preferably includehydrocarbons, such as toluene, xylene or hexane, chlorinatedhydrocarbons, such as chlorobenzene, methylene chloride or chloroform,ketones, such as acetone or butanone, ethers, such as tetrahydrofuran,diethyl ether, methyl tert-butyl ether, dimethoxyethane or dioxane,nitrites, such as acetonitrile, amides, such as N,N-dimethylformamide orN-methylpyrrolidone, sulfoxides, such as dimethyl sulfoxide, sulfones,such as sulfolane, and also esters, such as ethyl acetate or methylacetate.

[0240] In the preparation processes, the reaction temperatures can bevaried within a wide temperature range. In general, the processes arecarried out between −30° C. and +150° C., preferably between −10° C. and+110° C.

[0241] When carrying out the process according to the invention, ingeneral from 1 to 10 mol, preferably from 1 to 5 mol, of the compoundsof the general formula (II) or (V) or (VII) are employed per mole of thestarting material of the general formula (II) or (IV) or (VI). Work-upis carried out by customary methods.

[0242] Suitable for use as acid binders are both organic and inorganicbases. Suitable inorganic bases are carbonates, hydroxides, phosphatesand hydrides of the alkali metals, alkaline earth metals and transitionmetals; preference is given to using the carbonates and hydrides of thealkali metals and alkaline earth metals. Particular preference is givento potassium carbonate, sodium carbonate and caesium carbonate, and alsoto sodium hydride and potassium hydride. Suitable for use as organicbases are primary, secondary and tertiary amines. Preference is given totertiary amines, such as trimethylamine, triethylamine, tributylamine,DBU, DBN and pyridine or N,N-dimethylaniline.

[0243] The diazotizations can be carried out in the presence of analkali metal nitrite or an alkyl nitrite. Suitable for use as alkalimetal nitrite are all customary alkali metal nitrites; preference isgiven to using sodium nitrite or potassium nitrite. Suitable for use asalkyl nitrite are all customary alkyl nitrites which, preferably, have 1to 10 carbon atoms, in particular methyl nitrite, ethyl nitrite,n-propyl nitrite, isopropyl nitrite and isoamyl nitrite. Suitable foruse as catalyst are copper, copper salts, palladium or palladium salts.Preference is given to copper turnings, copper(I) iodide, palladium(II)acetate or tetrakis(triphenylphosphine)palladium(0).

[0244] The process according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to operate atreduced or elevated pressure, namely in the range from 0.1 to 10 bar.

[0245] Suitable for use as leaving groups are the esters of sulfonicacids, in particular mesylates, tosylates or triflates.

[0246] The novel and known compounds of the formula (I) have potentmicrobicidal action and can be used for controlling undesirablemicroorganisms, such as fungi and bacteria, in the protection ofmaterials.

[0247] In the protection of materials, the substances according to theinvention can be used for protecting industrial materials against attackand destruction by undesirable microorganisms.

[0248] In the present context, industrial materials are to be understoodas meaning non-live materials which have been prepared for use inindustry. For example, industrial materials can be glues, sizes, paperand board, textiles, leather, wood, wooden materials, paints andsynthetic articles, cooling lubricants and other materials which can beattacked or destroyed by microorganisms. Parts of production plants, forexample cooling-water circuits, which may be impaired by themultiplication of microorganisms may also be understood as industrialmaterials in the context of the present invention. Industrial materialswhich are preferably to be protected are glues, sizes, paper and boards,leather, wood, plastics, paints, cooling lubricants and heat transferliquids.

[0249] The compounds (I) to be used according to the invention areparticularly suitable for protecting wood, plastics, paints and coolinglubricants against attack by microorganisms.

[0250] Examples of microorganisms which are capable of bringing aboutdegradation of, or change in, the industrial materials and which may bementioned are bacteria, fungi, yeasts, algae and slime organisms. Theactive compounds according to the invention preferably act againstfungi, in particular moulds, wood-discolouring and wood-destroying fungi(Basidiomycetes) and also against slime organisms and algae.

[0251] Microorganisms of the following genera may be mentioned by way ofexample:

[0252] Alternaria, such as Alternaria tenuis,

[0253] Aspergillus, such as Aspergillus niger,

[0254] Chaetomium, such as Chaetomium globosum,

[0255] Coniophora, such as Coniophora puetana,

[0256] Lentinus, such as Lentinus tigrinus,

[0257] Penicillium, such as Penicillium glaucum,

[0258] Polyporus, such as Polyporus versicolor,

[0259] Aureobasidium, such as Aureobasidium pullulans,

[0260] Sclerophoma, such as Sclerophoma pityophila,

[0261] Trichoderma, such as Trichoderma viride,

[0262] Escherichia, such as Escherichia coli,

[0263] Pseudomonas, such as Pseudomonas aeruginosa,

[0264] Staphylococcus, such as Staphylococcus aureus.

[0265] Depending on their particular physical and/or chemicalproperties, the active compounds can be converted to the customaryformulations, such as solutions, emulsions, suspensions, powders, foams,pastes, granules, aerosols and microencapsulations in polymericsubstances and in coating compositions for seeds, and ULV cool andwarm-fogging formulations.

[0266] These formulations are produced in a known manner, for example bymixing the active compounds with extenders, that is, liquid solvents,liquefied gases under pressure, and/or solid carriers, optionally withthe use of surfactants, that is emulsifiers and/or dispersants, and/orfoam formers. If the extender used is water, it is also possible toemploy, for example, organic solvents as auxiliary solvents. Suitableliquid solvents are essentially: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample petroleum fractions, alcohols such as butanol or glycol andtheir ethers and esters, ketones such as acetone, methyl ethyl ketone,methyl isobutyl ketone or cyclohexanone, strongly polar solvents such asdimethylformamide or dimethyl sulfoxide, or else water. Liquefiedgaseous extenders or carriers are to be understood as meaning liquidswhich are gaseous at standard temperature and under atmosphericpressure, for example aerosol propellants such as halogenatedhydrocarbons, or else butane, propane, nitrogen and carbon dioxide.Suitable solid carriers are: for example ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals such as highlydisperse silica, alumina and silicates. Suitable solid carriers forgranules are: for example crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, or else syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, maize cobs and tobacco stalks.Suitable emulsifiers and/or foam formers are: for example nonionic andanionic emulsifiers, such as polyoxyethylene fatty acid esters,polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulfonates, alkyl sulfates, arylsulfonates, or else proteinhydrolysates. Suitable dispersants are: for example lignin-sulfite wasteliquors and methylcellulose.

[0267] Tackifiers such as carboxymethylcellulose and natural andsynthetic polymers in the form of powders, granules or latices, such asgum arabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

[0268] It is possible to use colorants such as inorganic pigments, forexample iron oxide, titanium oxide and Prussian Blue, and organicdyestuffs such as alizarin dyestuffs, azo dyestuffs and metalphthalocyanine dyestuffs, and trace nutrients such as salts of iron,manganese, boron, copper, cobalt, molybdenum and zinc.

[0269] The formulations generally comprise between 0.1 and 95 percent byweight of active compound, preferably between 0.5 and 90%.

[0270] The active compounds according to the invention, as such or intheir formulations, can also be used in a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, for example towiden the activity spectrum or to prevent the development of resistance.In many cases, synergistic effects are obtained, i.e. the activity ofthe mixture is greater than the activity of the individual components.

[0271] For applications in the protection of materials, the followingco-components, for example, are found to be particularly favourable:

[0272] imidazoles such as:

[0273] clotrimazole, bifonazole, climbazole, econazole, fenapamil,imazalil, isoconazole, ketoconazole, lombazole, miconazole, pefurazoate,prochloraz, triflumizole, thiazolcar,1-imidazolyl-1-(4′-chlorophenoxy)-3,3-dimethylbutan-2-one, and theirmetal salts and acid adducts;

[0274] triazoles such as:

[0275] azaconazole, azocyclotin, bitertanol, bromuconazole,cyproconazole, diclobutrazole, difenoconazole, diniconazole,epoxyconazole, etaconazole, fenbuconazole, fenchlorazole, fenethanil,fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole,imibenconazole, ipconazole, isozofos, metconazole, myclobutanil,paclobutrazol, penconazole, propioconazole,(±)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,tebuconazole, tetraconazole, triadimefon, triadimenol, triapenthenol,triflumizole, triticonazole, uniconazole and their metal salts and acidadducts;

[0276] pyridines and pyrimidines such as:

[0277] ancymidol, buthiobate, fenarimol, mepanipyrin, nuarimol,pyroxyfur, triamirol;

[0278] succinate dehydrogenase inhibitors such as:

[0279] benodanil, carboxim, carboxim sulfoxide, cyclafluramid, fenfuram,flutanil, furcarbanil, furmecyclox, mebenil, mepronil, methfuroxam,metsulfovax, pyrocarbolid, oxycarboxin, shirlan, Seedvax;

[0280] naphthalene derivatives such as:

[0281] terbinafine, naftifine, butenafine,3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine);

[0282] sulfenamides such as:

[0283] dichlofluanid, tolylfluanid, folpet, fluorofolpet, captan,captofol;

[0284] benzimidazoles such as:

[0285] carbendazim, benomyl, fuberidazole, thiabendazole or their salts;

[0286] morpholine derivatives such as:

[0287] aldimorph, dimethomorph, dodemorph, falimorph, fenpropidinfenpropimorph, tridemorph, trimorphamid and their arylsulfonate saltssuch as, for example, p-toluenesulfonic acid and p-dodecylphenylsulfonicacid;

[0288] benzothiazoles such as:

[0289] 2-mercaptobenzothiazole;

[0290] benzothiophene dioxides such as:

[0291] N-cyclohexyl-benzo[b]thiophene-S,S-dioxide carboxamide;

[0292] benzamides such as:2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, tecloftalam;

[0293] boron compounds such as:

[0294] boric acid, boric ester, borax;

[0295] formaldehyde and formaldehyde-releasing compounds such as:

[0296] benzyl alcohol mono-(poly)-hemiformal, n-butanol hemiformal,dazomet, ethylene glycol hemiformal, hexa-hydro-S-triazine,

[0297] hexamethylenetetramine, N-hydroxymethyl-N ′-methylthiourea,N-methyloichloroacetamide, oxazolidine, paraformaldehyde, taurolin,tetrahydro-1,3-oxazine, N-(2-hydroxypropyl)-amine-methanol;

[0298] isothiazolinones such as:

[0299] N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one,4,5-dichloro-N-octylisothiazolin-3-one, 5-chloro-N-octylisothiazolinone,N-octyl-isothiazolin-3-one, 4,5-trimethylene-isothiazolinone,4,5-benzoisothiazolinone;

[0300] aldehydes such as:

[0301] cinnamaldehyde, formaldehyde, glutardialdehyde,β-bromocinnamaldehyde;

[0302] thiocyanates such as:

[0303] thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate;

[0304] quaternary ammonium compounds and guanidines such as:

[0305] benzalkonium chloride, benzyldimethyltetradecylammonium chloride,benzyldimethyldodecylammonium chloride,dichlorobenzyl-dimethyl-alkyl-ammonium chloride, didecyidimethylammoniumchloride, dioctyl-dimethyl-ammonium chloride,N-hexadecyl-trimethyl-ammonium chloride, 1-hexadecyl-pyridiniumchloride, iminoctadine tris(albesilate);

[0306] iodine derivatives such as:

[0307] diiodomethyl p-tolyl sulfone, 3-iodo-2-propinyl alcohol,4-chloro-phenyl -3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 2,3,3-triiodoallyl alcohol,3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyln-butyl-carbamate, 3-iodo-2-propinyl n-hexylcarbamate,3-iodo-2-propinyl-cyclohexylcarbamate, 3-iodo-2-propinylphenylcarbamate;

[0308] phenols such as:

[0309] tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol,3,5-dimethyl -4-chlorophenol, phenoxyethanol, dichlorophene,2-benzyl-4-chlorophenol, 5-chloro-2-(2,4-dichlorophenoxy)-phenol,hexachlorophene, p-hydroxybenzoate, o-phenylphenol, m-phenylphenol,p-phenylphenol and their alkali metal salts and alkaline earth metalsalts;

[0310] microbicides with an activated halogen group such as:

[0311] bronopol, bronidox, 2-bromo-2-nitro-1,3-propanediol,2-bromo-4′-hydroxy-acetophenone,1-bromo-3-chloro-4,4,5,5-tetramethyl-2-imidazolidinone,β-bromo-β-nitrostyrene, chloracetamid, chloramin T,1,3-dibromo-4,4,5,5-tetramethyl-2-imidazolidinone, dichloramin T,3,4-dichloro-(3H)-1,2-dithiol-3-one, 2,2-dibromo-3-nitrile-propionamide,1,2-dibromo-2,4-dicyanobutane, halane, halazone, mucochloric acid,phenyl (2-chlorocyano-vinyl) sulfone, phenyl (1,2-dichloro-2-cyanovinyl)sulfone, trichloroisocyanuric acid;

[0312] pyridines such as:

[0313] 1-hydroxy-2-pyridinethione (and their Na, Fe, Mn, Zn salts),tetra-chloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim,dipyrithion,1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridine;

[0314] methoxyacrylates or similar such as:

[0315] azoxystrobin,

[0316] methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate,

[0317] (E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide,

[0318](E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate,

[0319] O-methyl2-[([3-methoximino-2-butyl)imino]oxy)o-tolyl]-2-methoximino-acet-imidate,

[0320]2-[[[[1-(2,5-dimethylphenyl)ethylidene]amino]oxy]methyl]-alpha-(methoximino)-N-methylbenzeneacetamide,

[0321]alpha-(methoxyimino)-N-methyl-2-[[[[1-[3-(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]-benzeneacetamide,

[0322] trifloxystrobin,

[0323]alpha-(methoxymethylene)-2-[[[[1-[3-(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]-benzeneaceticacid methyl ester,

[0324]2-[[[5-chloro-3-(trifluoromethyl)-2-pyridinyl]oxy]methyl]-alpha-(methoxyimino)-N-methylbenzeneacetamide,

[0325]2-[[[cyclopropyl[(4-ethoxyphenyl)imino]methyl]thio]methyl]-alpha-(methoxyimino)-benzeneaceticacid methyl ester,

[0326]alpha-(methoxyimino)-N-methyl-2-(4-methyl-5-phenyl-2,7-dioxa-3,6-diazaocta-3,5-dien-1-yl)-benzeneacetamide,

[0327]alpha-(methoxymethylene)-2-(4-methyl-5-phenyl-2,7-dioxa-3,6-diazaocta-3,5-dien-1-yl)-benzeneaceticacid methyl ester,

[0328]alpha-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]-methyl]-benzeneacetamide,

[0329]2-[[(3,5-dichloro-2-pyridinyl)oxy]methyl]-alpha-(methoxyimino)-N-methyl-benzeneacetamide,

[0330]2-[4,5-dimethyl-9-(4-morpholinyl)-2,7-dioxa-3,6-diazanona-3,5-dien-1-yl]-alpha-(methoxymethylene)-benzeneaceticacid methyl ester, kresoxim-methyl;

[0331] metal soaps such as:

[0332] tin naphthenate, copper napthenate, zinc napthenate, tin octoate,copper octoate, zinc octoate, tin 2-ethylhexanoate, copper2-ethylhexanoate, zinc 2-ethylhexanoate, tin oleate, copper oleate, zincoleate, tin phosphate, copper phosphate, zinc phosphate, tin benzoate,copper benzoate, zinc benzoate;

[0333] metal salts such as:

[0334] copper hydroxycarbonate, sodium dichromate, potassium dichromate,potassium chromate, copper sulfate, copper chloride, copper borate, zincfluorosilicate, copper fluorosilicate;

[0335] oxides such as:

[0336] tributyltin oxide, Cu₂O, CuO, ZnO;

[0337] dithiocarbamates such as:

[0338] cufraneb, ferban, potassiumN-hydroxymethyl-N′-methyl-dithiocarbamate, sodiumdimethyldithiocarbamate, potassium dimethyldithiocarbamate, macozeb,maneb, metam, metiram, thiram, zineb, ziram;

[0339] nitriles such as:

[0340] 2,4,5,6-tetrachloroisophthalonitrile, disodiumcyano-dithioimidocarbamate;

[0341] quinolines such as:

[0342] 8-hydroxyquinoline and its copper salts;

[0343] other fungicides and bactericides such as:

[0344] 5-hydroxy-2(5H)-furanone, 4,5-benzodithiazolinone,4,5-trimethylenedithiazolinone, N-(2-p-chlorobenzoylethyl)-hexaminiumchloride, 2-oxo-2-(4-hydroxy-phenyl)-acetohydroxamic acid chloride,tris-N-(cyclohexyldiazeniumdioxy)-aluminium,N-(cyclohexyldiazeniumdioxy)-tributyltin or its potassium salts,bis-N-(cyclohexyldiazeniumdioxy)-copper, iprovalicarb, fenhexamid,spiroxamine, carpropamid, diflumetorin, quinoxyfen, famoxadone,polyoxorim, acibenzolar S-methyl, furametpyr, thifluzamide,methalaxyl-M,

[0345] Ag-, Zn- or Cu-containing zeolites alone or incorporated intopolymeric materials.

[0346] Very especially preferred are mixtures of compounds of theformula (I) to be used according to the invention with one or more ofthe following active compounds:

[0347] azaconazole, bromuconazole, cyproconazole, dichlobutrazol,diniconazole, hexaconazole, metaconazole, penconazole, propiconazole,tebuconazole, dichlofluanid, tolylfluanid, fluorfolpet, methfuroxam,carboxin, benzo[b]thiophene S,S-dioxide N-cyclohexylcarboxamide,fenpiclonil,4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile,butenafine, imazalil, N-methyl-isothiazolin-3-one,5-chloro-N-methylisothiazolin -3-one, N-octylisothiazolin-3-one,dichloro-N-octylisothiazolinone, mercaptobenthiazole,thiocyanatomethylthiobenzothiazole, benzoisothiazolinone,N-(2-hydroxypropyl)-amino-methanol, benzyl alcohol (hemi)-formal,N-methylolchloroacetamide, N-(2-hydroxypropyl)-amine-methanol,glutaraldehyde, omadine, dimethyl dicarbonate, 2-bromo-2-nitro-1,3-propanediol and/or 3-iodo-2-propinyl n-butylcarbamate.

[0348] Apart from with the abovementioned fungicides and bactericides,mixtures with a good efficacy are, moreover, also prepared, for examplewith one or more of the following active compounds:

[0349] insecticides/acaricides/nematicides:

[0350] abamectin, acephate, acetamiprid, acrinathrin, alanycarb,aidicarb, aidoxycarb, aldrin, allethrin, alpha-cypermethrin, amitraz,avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin,

[0351]Bacillus thuringiensis, barthrin,4-bromo-2(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile,bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin,bioresmethrin,

[0352] bioallethrin, bromophos A, bromophos M, bufencarb, buprofezin,butathiophos, butocarboxin, butoxycarboxim,

[0353] cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,cartap, quinomethionate, cloethocarb, chlordane, chlorethoxyfos,chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos,N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-ethaneimidamide,chlorpicrin, chlorpyrifos A, chlorpyrifos M, cis-resmethrin, clocythrin,cypophenothrin, clofentezin, coumaphos, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazin,

[0354] decamethrin, deltamethrin, demeton M, demeton S,demeton-S-methyl, diafenthiuron, dialiphos, diazinon,1,2-dibenzoyl-1(1,1-dimethyl)-hydrazine, DNOC, dichlofenthion,dichlorvos, dicliphos, dicrotophos, difethialone, diflubenzuron,dimethoate, dimethyl-(phenyl)-silyl-methyl 3-phenoxybenzyl ether,dimethyl-(4-ethoxyphenyl)-silylmethyl-3-phenoxybenzyl ether,dimethylvinphos, dioxathion, disulfoton,

[0355] eflusilanate, emamectin, empenthrin, endosulfan, EPN,esfenvalerate, ethiofencarb, ethion, ethofenprox, etrimphos, etoxazole,etobenzanid, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin,fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin,fenpyrad, fenpyroximat, fensulfothion, fenthion, fenvalerate, fipronil,fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flupyrazofos,flufenzine, flumethrin, flufenprox, fluvalinate, fonophos, formethanate,formothion, fosmethilan, fosthiazate, fubfenprox, furathiocarb,

[0356] halofenocid, HCH, heptenophos, hexaflumuron, hexythiazox,hydramethylnon, hydroprene,

[0357] imidacloprid, imiprothrin, indoxycarb, iodfenfos, iprinomectin,iprobenfos, isazophos, isoamidophos, isofenphos, isoprocarb,isoprothiolane, isoxathion, ivermectin, lama-cyhalothrin, lufenuron,

[0358] kadedrin

[0359] lambda-cyhalothrin, lufenuron,

[0360] malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde,methacrifos, methamidophos, methidathion, methiocarb, methomyl,metalcarb, milbemectin, monocrotophos, moxiectin,

[0361] naled, NC 184, NI 125, nicotine, nitenpyram,

[0362] omethoate, oxamyl, oxydemethon M, oxydeprofos,

[0363] parathion A, parathion M, penfluron, permethrin,2-(4-phenoxyphenoxy)-ethyl ethylcarbamate, phenthoate, phorate,phosalon, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,pirimiphos A, prallethrin, profenophos, promecarb, propaphos, propoxur,prothiophos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion,pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,pyrithiobac-sodium,

[0364] quinalphos,

[0365] resmethrin, RH-7988, rotenone,

[0366] salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,

[0367] tau-fluvalinate, taroils, tebufenozide, tebufenpyrad,tebupirimphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos,tetrachlorvinphos, tetramethrin, tetramethacarb, thiacloprid, thiafenox,thiamethoxam,

[0368] thiapronil, thiodicarb, thiofanox, thiazophos, thiocyclam,thiomethon, thionazin, thuringiensin, tralomethrin, transfluthrin,triarathen, triazophos, triazamate, triazuron, trichlorfon, triflumuron,trimethacarb,

[0369] vamidothion, XMC, xylylcarb, zetamethrin;

[0370] molluscicides

[0371] fentin acetate, metaldehyde, methiocarb, niclosamide;

[0372] herbicides and algicides

[0373] acetochlor, acifluorfen, aclonifen, acrolein, alachlor,alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate,anilofos, asulam, atrazine, azafenidin, aziptrotryne, azimsulfuron,

[0374] benazolin, benfluralin, benfuresate, bensulfuron, bensulfide,bentazone, benzofencap, benzthiazuron, bifenox, bispyribac, borax,bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butamifos,butralin, butylate, bialaphos, benzoyl-prop, bromobutide, butroxydim,

[0375] carbetamide, carfentrazone-ethyl, carfenstrole, chlomethoxyfen,chloramben, chlorbromuron, chlorflurenol, chloridazon, chlorimuron,chlornitrofen, chloroacetic acid, chloransulam-methyl, cinidon-ethyl,chlorotoluron, chloroxuron, chlorpropham, chlorsulfuron, chlorthal,chlorthiamid, cinmethylin, cinofulsuron, clefoxydim, clethodim,clomazone, chlomeprop, clopyralid, cyanamide, cyanazine, cycloate,cycloxydim, chloroxynil, clodinafop-propargyl, cumyluron, CGA 248757,clometoxyfen, cyhalofop, cyhalofop-butyl, clopyrasuluron,cyclosulfamuron,

[0376] diclosulam, dichlorprop, dichlorprop-P, diclofop, diethatyl,difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron,dimepiperate, dimethachlor, dimethipin, dinitramine, dinoseb, dinosebacetate, dinoterb,

[0377] diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, DSMA,2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn,dicamba, dichlobenil, dimethamid, dithiopyr, dimethametryn,

[0378] eglinazine, endothal, EPTC, esprocarb, ethalfluralin,ethidimuron, ethofumesate, ethobenzanid, ethoxyfen, ET 751,ethametsulfuron, ethoxysulfuron,

[0379] fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M,flazasulfuron, fluazifop, fluazifop-P, fuenachlor, fluchloralin,flufenacet, flumeturon, fluorocglycofen, fluoronitrofen, flupropanate,flurenol, fluridone, flurochloridone, fluroxypyr, fomesafen, fosamine,flamprop-isopropyl, flamprop-isopropyl-L, flumiclorac-pentyl,flumipropyn, flumioxzim, flurtamone, flumioxzim, flupyrsulfuron-methyl,

[0380] glyphosate, glufosinate-ammonium

[0381] haloxyfop, hexazinone,

[0382] imazamethabenz, isoproturon, isoxaben, isoxapyrifop, imazapyr,imazaquin, imazethapyr, ioxynil, isopropalin, imazosulfuron, imazomox,isoxaflutole, imazapic,

[0383] KUH 911, KUH 920

[0384] lactofen, lenacil, linuron, LS830556,

[0385] MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet,mefluidide, metam, metamitron, metazachlor, methabenzthiazuron,methazole, methoroptryne, methyldymron, methyl isothiocyanate,

[0386] metobromuron, metoxuron, metribuzin, metsulfuron, molinate,monalide, monolinuron, MSMA, metolachlor, metosulam, metobenzuron,

[0387] naproanilide, napropamide, naptalam, neburon, nicosulfuron,norflurazon, sodium chlorate,

[0388] oxadiazon, oxyfluorfen, oxysulfuron, orbencarb, oryzalin,oxadiargyl,

[0389] propyzamide, prosulfocarb, pyrazolate, pyrazolsulfuron,pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, paraquat, pebulate,pendimethalin, pentachlorophenol, pentoxazone, pentanochlor, petroleumoils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron,prodiamine, prometryn, propachlor, propanil, propaquizafob, propazine,propham, propisochlor, pyriminobac-methyl, pelargonic acid, pyrithiobac,

[0390] quinmerac, quinocloamine, quizalofop, quizalofop-P, quinchlorac,

[0391] rimsulfuron

[0392] sethoxydim, sifuron, simazine, simetryn, sulfosulfuron,sulfometuron, sulfentrazone, sulcotrione, sulfosate,

[0393] tar oils, TCA, tebutam, tebuthiuron, terbacil, terbumeton,terbuthylazine, terbutryn, thiazafluoron, thifensulfuron, thiobencarb,thiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron,triclopyr, tridiphane, trietazine, trifluralin, tycor, thdiazimin,thiazopyr, triflusulfuron,

[0394] vernolate.

[0395] The active compounds can be applied as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. Application is carried out in a customary manner, forexample by watering, spraying, atomizing, broadcasting, dusting,foaming, spreading-on and the like.

[0396] The compositions used for protecting industrial materialsgenerally comprise the active compounds in an amount of from 1 to 95%,preferably from 10 to 75%.

[0397] The use concentrations of the active compounds according to theinvention depend on the type and the occurrence of the microorganisms tobe controlled, and on the composition of the material to be protected.The optimal rate can be determined by test series. In general, the useconcentrations are in the range from 0.001 to 5% by weight, preferablyfrom 0.05 to 1.0% by weight, based on the material to be protected.

[0398] The invention is further described in the following illustrativeexamples in which all parts and percentages are by weight unlessotherwise indicated

EXAMPLES Preparation Examples Example 1

[0399] 3.2 g (0.02 mol) of methyl1,3-thiazolidine-2-thione-4-carboxylate are initially charged inacetonitrile, and 2.27 g (0.022 mol) of triethylamine and subsequently3.43 g (0.022 mol) of ethyl iodide are added. The reaction mixture isstirred at room temperature for 4 days, water is added and the mixtureis extracted. The crude product obtained after drying of the organicphase and concentration is chromatographed, giving the thiazole of thegeneral formula (I) where R1=ethyl, R2=CO₂Me and n=1 as a pale yellowoil.

[0400] Yield: 2.0 g (49% of theory), n_(D) ²⁶=1.5485

Example 2

[0401] K₂CO₃ (2.07 g, 0.015 mol) is initially charged in acetonitrile,and 1,3-thiazolidine-2-thione (1.19 g, 0.01 mol) in acetonitrile isadded. 2-Chloro-1-(1H-pyrrol-2-yl)ethanone (1.43 g, 0.01 mol) isdissolved in acetonitrile and metered in. The reaction mixture isstirred at room temperature for 16 h and heated at 40° C. for another 8h. The solid is filtered off, the reaction mixture is concentrated andthe residue is taken up in CH₂Cl₂ and washed with water. Drying andconcentration give the thiazine of the general formula (I) where R¹=

[0402] R²=H and n=1.

[0403] Yield: 1.7 g (65% of theory) m.p.=103-105° C.

Example 3

[0404] 2-Mercaptothiophene (0.56 g, 5.75 mmol) and triethylamine (0.58g, 5.75 mmol) are initially charged in acetone (50 ml), and the mixtureis stirred at room temperature for about 10 minutes. 1.0 g (5.75 mmol)of 1-bromo-2-isothiocyanatoethane is added. The reaction mixture isstirred under reflux for 4 h, water is added and the mixture isextracted. The organic phase is dried and concentrated, giving thethiazole of the general formula (I) where R¹=

[0405] R²=H and n=1 as an oil.

[0406] Yield: 0.69 g (60% of theory), δ (CDCl₃)=3.30 (m, 2H), 4.30 (m,2H), 7.05-7.60 (m, 3H)

Example 4

[0407] 1.85 g (0.015 mol) of p-methoxyaniline are suspended in water (25ml), acidified using conc. hydrochloric acid (3.8 ml) and cooled to 0°C. A solution of 1.10 g (0.016 mol) of sodium nitrite in water (about 8ml) is added dropwise. The solution is stirred at 0° C. for 1 h and thenadjusted to about pH 4.5-5 using sodium acetate. At 0° C., this solutionis added dropwise to a solution of 2.43 g (0.015 mol) of methyl1,3-thiazolidine-2-thione-4-carboxylate in acetone (75 ml) and water (6ml) containing 0.6 g of sodium hydroxide and 4.4 g of sodium acetate.The reaction mixture is stirred at this temperature for 1 h, water isadded and the mixture is extracted. The residue that remains afterdrying and concentration is chromatographed, giving the thiazole of thegeneral formula (I) where R1=p-MeOC₆H₄, R2=CO₂Me and n=1 as an oil.

[0408] Yield: 1.13 g (27% of theory); n_(D) ²⁶=1.5990

Example 5

[0409] 34.42 g (0.2 mol) of 2-chloro-5,6-dihydro-4H-1,3-thiazinehydrochloride are dissolved in water and adjusted to about pH 10 usingK₂CO₃. The solution is stirred for 30 minutes and extracted with ethylacetate. The organic phase is dried and evaporated to dryness underreduced pressure. The oil is dissolved in DMF. Under an atmosphere ofnitrogen, this solution is added dropwise to a suspension of 21.95 g(0.191 mol) of 2-mercapto-thiophene and 8.39 g (0.21 mol) of sodiumhydride in DMF which had been stirred at room temperature for 30minutes, and the mixture is stirred at 100C for 4.5 hours and at roomtemperature for 16 h. Water is added, and the mixture is extracted withethyl acetate. The organic phase is dried and concentrated. The residueis chromatographed, giving the thiazine of the general formula (I) whereR¹=

[0410] R²=H and n=2.

[0411] Yield: 0.5 g (20% of theory), n_(D) ²⁰=1.5660

Example 6

[0412] 2.5 g (0.021 mol) of 1,3-thiazine-2-thione and 3.17 g (0.023 mol)of K₂CO₃ are together initially charged in acetonitrile. 0.032 mol ofoctyl bromide is added dropwise to the suspension. The reaction mixtureis stirred at room temperature for 16 h, water is added and the mixtureis extracted with ethyl acetate. The organic phase is dried andconcentrated. The residue is separated by column chromatography, givingthe thiazine of the general formula (I) where R1=n-octyl, R2=H and n=2.

[0413] Yield: 1.08 g (21% of theory), n_(D) ²⁰=1.5465

[0414] The substances of the general formula (I) listed in Table 1 areprepared analogously to Examples 1 to 6 and/or in accordance with thegeneral statements in the description of the experiments. TABLE 1Example R¹ R² n Physical data 7 propyl CO₂Me 1 n_(D) ²⁶ = 1.5445 8iso-propyl CO₂Me 1 n_(D) ²⁶ = 1.5440 9 cyclo-pentyl CO₂Me 1 n_(D) ²⁶ =1.5755 10 EtO—CO—CH₂ CO₂Me 1 n_(D) ²⁶ = 1.5350 11 C₆H₅—CO—CH₂ CO₂Me 1n_(D) ²⁶ = 1.6210 12

H 1 δ(CDCl₃) = 1.45(m, 2H), 1.75(m, 2H), 3.40(m, 2H), 4.15(m, 2H),4.50(s, 2H) 13 3,4-Cl₂C₆H₃ H 1 δ(CDCl₃) = 3.38(m, 2H), 4.25(m, 2H),7.4-7.7(m, 3H) 14 4-CF₃O—C₆H₄ H 1 δ(CDCl₃) = 3.35(m, 2H), 4.30(m, 2H),7.20-7.6(m, 4H) 15 4-CH₃C₆H₄ CO₂Me 1 δ(CDCl₃) = 2.35(s, 3H), 3.50(m,2H), 3.80(s, 3H), 5.15(m, 1H), 7.20-7.55(m, 4H) 16 C₆H₅ CO₂Me 1 n_(D) ²⁶= 1.6140 17 4-BrC₆H₄ CO₂Me 1 m.p. = 99.5° C. 18 3-ClC₆H₄ CO₂Me 1δ(CDCl₃) = 3.58(m, 2H), 3.80(s, 3H), 5.15(m, 1H), 7.15-7.75(m, 4H) 19

H 1 m.p. = 72° C. 20 EtOCH₂ H 1 δ(CDCl₃) = 1.20(t, 3H), 3.30 (m, 2H),3.65(m, 3H), 4.15 (m, 2H), 5.18(s, 2H) 21

H 1 δ(CDCl₃) = 3.45(m, 2H), 4.20(m, 2H), 4.55(s, 2H), 7.15-7.85(m, 3H)22 benzyl H 2 δ(CDCl₃) = 2.20(m, 2H), 2.95(m, 2H), 3.45(m, 2H), 5.38(s,2H), 7.2-7.45(m, 5H) 23 EtOCH₂ H 2 m.p. = 49° C. 24 butyl H 2 n_(D) ²³ =1.6028 25 3-MeOC₆H₄ H 2 n_(D) ²³ = 1.5795 26 2-MeOC₆H₄ H 2 m.p. = 165°C. 27

H 2 n_(D) ²³ = 1.5485 28

H 2 m.p. = 66-67° C. 29

H 2 n_(D) ²³ = 1.5680 30 4-MeO—C₆H₄— H 2 m.p. = 102-103° C. CO—CH₂ 31allyl H 2 δ(CDCl₃) = 2.30(m, 2H), 3.00(m, 2H), 3.45(m, 2H), 4.75(m, 2H),5.28(m, 2H), 5.85(m, 1H) 32

H 2 m.p. = 65-66° C. 33 4-CF₃O—C₆H₄ H 2 δ(CDCl₃) = 1.85(m, 2H), 3.05(m,2H), 3.75(m, 3H), 7.15-7.60(m, 4H) 34

H 2 m.p. = 114.5° C. 35 3-MeO—C₆H₄ H 2 R_(f) = 0.44 (toluene 5, ethylacetate 1) 36 2-MeO—C₆H₄ H 2 R_(f) = 0.30 (toluene 5, ethyl acetate 1)37 2,6-Me₂—C₆H₃ H 2 m.p. = 205° C. 38 4-HO—C₆H₄ H 2 m.p. = 210° C. 393-FC₆H₄ H 2 R_(f) = 0.32 (toluene 10, ethyl acetate 1) 40 4-CF₃—C₆H₄ H 2m.p. = 125° C. 41 3-HO—C₆H₄ H 2 m.p. = 197° C. 42 3,4-(MeO)₂—C₆H₃ H 2R_(f) = 0.24 (toluene 10, ethyl acetate 1) 43 3-CF₃—C₆H₄ H 2 R_(f) =0.48 (toluene 1, ethyl acetate 1) 44 4-C₂H₅—C₆H₄ H 2 R_(f) = 0.32(toluene 10, ethyl acetate 1) 45 4-(C₆H₅O)—C₆H₄ H 2 R_(f) = 0.43(toluene 10, ethyl acetate 1) 46 3-(C₆H₅O)—C₆H₄ H 2 R_(f) = 0.41(toluene 10, ethyl acetate 1) 47 4-(C₆H₅)—C₆H₄ H 2 R_(f) = 0.46 (toluene10, ethyl acetate 1) 48 3-(C₆H₅)—C₆H₄ H 2 R_(f) = 0.44 (toluene 10,ethyl acetate 1) 49 4-(cyclo-propyl)- H 2 R_(f) = 0.07 (toluene) C₆H₄

Use Example A

[0415] To demonstrate the activity against bacteria, the minimuminhibitory concentrations (MIC) of the agents according to the inventionare determined:

[0416] The active compounds according to the invention are in each caseadded, in concentrations of from 0.1 mg/ml to 5000 mg/ml, to achemically defined nutrient agar. After the agar has solidified, it iscontaminated with pure cultures of the test organisms listed in Table 2.The MIC is determined after 3 days of incubation at 28° C. and 60 to 70%relative atmospheric humidity. MIC is the lowest concentration of activecompound at which the microbial species used does not grow at all; it isstated in Table 2. TABLE 2 Minimum inhibitory concentration (ppm) of thecompounds of the formula (I) according to the invention Example No./CASNo. Bacillus subtilis 22 100 73122-32-4 <100 27 <100 73122-35-7 <4073122-37-9 100  8 <200 3571-74-2 200

Use Example B

[0417] To demonstrate the activity against fungi, the minimum inhibitoryconcentrations (MIC) of agents according to the invention aredetermined:

[0418] The active compounds according to the invention are in each caseadded, in concentrations of from 0.1 mg/l to 5 000 mg/l, to an agarwhich is prepared using malt extract. After the agar has solidified, itis contaminated with pure cultures of the test organisms listed in Table3. The MIC is determined after 2 weeks of incubation at 28° C. and 60 to70% relative atmospheric humidity.

[0419] MIC is the lowest concentration of active compound at which themicrobial species used does not grow at all; it is stated in Table 3.

[0420] Table 3 Minimum Inhibitory Concentrations (ppm) of Compounds ofthe Formula (I) According to the Invention TABLE 3 Example No./Penicillium Chaetomium Aspergillus CAS No. brevicaule globosum niger73122-32-4 <200 <200 <300 10554-28-6 <200 <200 <400 73122-49-3 <300 <400<400 73122-33-5 <200 <200 200 73122-44-8 <100 <200 <250 73122-52-8 <200<100 <150 73122-34-6 <100 <100 400 55545-14-7 <200 <200 <200 26 100 200 5 <100 <100 <200 32 <200 <200 73122-41-5 <200 <200 <300 73122-45-9 <100<100 <200 103482-99-1 <200 <200 103482-92-4 200 <200 103482-93-5 200<200 18 200 754-1-1 200 100 822-1-1 <200 <300 73122-51-7 100 <100 20073122-48-2 <100 <100 100 73122-46-0 100 <200 200 73122-42-6 <50 <100 10036 100 100 100 39 <100 <100 100 44 <100 <100 100 37 400 <200 40 <100<100 <250 41 100 200 42 <200 100 500 45 100 <100 48 200 <100 49 <100<100 100

Use Example C

[0421] To test dispersion coatings for resistance to mould, thefollowing procedure is adopted:

[0422] The paint to be tested is applied to both sides of a suitablebase. To obtain results which are close to practice, some of the testspecimens are leached out with running water (24 h, 20° C.) before thetest for mould resistance; others are treated with a current of warmfresh air (7 days, 40° C.).

[0423] The samples prepared in this way are then placed on an agarnutrient medium, and both samples and nutrient medium are contaminatedwith fungal spores. After 2-3 weeks storage (29±1° C., 80-90% rel.atmospheric humidity), the samples are compared.

[0424] The coating is considered to be permanently mould-resistant ifthe sample remains free from fungus or at most a slightly borderinfestation can be detected.

[0425] For the contamination, fungal spores of the following mould fungiare used, which are known as paint destroyers or are frequentlyencountered on coatings:

[0426]Alternaria tenius

[0427]Aspergillus flavus

[0428]Aspergillus niger

[0429]Aspergillus ustus

[0430]Cindosporum herbarum

[0431]Paecilomyces variotii

[0432]Penicillium citrium

[0433]Aureobasidium pullulans

[0434]Stachybotrys chartarum

[0435] Coatings according to recipe A are mould-resistant (even afterleaching out and wind tunnel exposure) if they contain, for example,1.5% (based on solids) of the compound of Example 25.

[0436] Recipe A: Exterior Dispersion Paint Based on Acroal 290 D(Styrene Acrylate) Parts by Tradename weight Chemical name Bayer TitanRKB2 40 Titanium dioxide Talkum V58 new 10 Magnesium silicate,containing water Durcal 5 45 Calcite CaCO₃ Walsroder MC 3000 S 2% 30Methylcellulose H₂O 6.5 Distilled water Calgon N 10% 3 PolyphosphatePigmentverteiler A 10% 1 Polyacrylic acid salt Agitan 281, 1:1 inTexanol 1 White spirit 5 Mixture of aliph. hydrocarbons Butyl glycolacetate 1.5 Butyl glycol acetate Acronal 290 D (binder) 71 Polyacrylicacid ester Total 219

[0437] Although the present invention has been described in detail withreference to certain preferred versions thereof, other variations arepossible. Therefore, the spirit and scope of the appended claims shouldnot be limited to the description of the versions contained therein.

What is claimed is:
 1. A method comprising treating an industrialmaterial with a compound of the formula (I)

wherein R¹ represents hydrogen or in each case optionally substitutedalkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl, R² representshydrogen, alkoxycarbonyl or alkylcarbonyl and n represents 1 or 2, andthereby protecting the industrial material.
 2. The method according toclaim 1, wherein in formula (I) R¹ represents hydrogen or representsC₁-C₁₂-alkyl which is optionally mono- or polysubstituted by identicalor different substituents from the group consisting of C₁-C₆-alkoxy;C₁-C₆-alkoxycarbonyl; in each case optionally halogen- and/orC₁-C₆-alkoxy-substituted phenyl or phenylcarbonyl; C₁-C₆-alkylcarbonyl;optionally halogen-substituted C₃-C₈-cycloalkylcarbonyl; 5- or6-membered heterocyclylcarbonyl having 1 to 3 heteroatoms from the groupconsisting of N, O and S; 5- or 6-membered heterocyclylthio having 1 to3 heteroatoms from the group consisting of N, O and S; or representsC₂-C₆-alkenyl, C₂-C₆-alkinyl, C₃-C₈-cycloalkyl or represents phenylwhich is optionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen, C₁-C₆-alkyl,C₃-C₈-cycloalkyl, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₁-C₆-alkoxy,nitro, nitrile, hydroxyl, amino, phenoxy, phenyl anddi-C₁-C₆-alkylamino, or represents a 5- or 6-membered heterocycle having1 to 3 identical or different heteroatoms from the group consisting ofO, S, N, which heterocycle optionally contains a fused-on aromatic6-membered ring, R² represents hydrogen, C₁-C₆-alkoxycarbonyl or C₁-C₆-alkylcarbonyl, and n represents 1 or
 2. 3. The method accordingto claim 1, wherein the industrial material protected against attack bymicroorganisms is selected from the group consisting of woods, paints,plastics, cooling lubricants, and combinations thereof.
 4. The methodaccording to claim 1, wherein the industrial material is wood or timberand the wood or timber are protected against attack by wood-destroyingand/or wood-discolouring fungi.
 5. A compound of the formula (I):

wherein R¹ represents hydrogen or in each case optionally substitutedalkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl, R² representshydrogen, alkoxycarbonyl or alkylcarbonyl and n represents 1 or 2,except for 2-(phenylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,2-[(3-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(4-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-(methylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,2-[(4-methoxyphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(4-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-(ethylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,2-[(4-nitrophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(3,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(2-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-1-phenylethanone,2-{[3-(trifluoromethyl)-1,2,4-thiadiazol-5-yl]sulfanyl}-5,6-dihydro-4H-1,3-thiazine,2-[(2,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(4-bromophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(2,6-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(3,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(3-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,4-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-N,N-dimethylaniline,2-[(4-fluorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine, methyl2-(methylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate, methyl2-(4-chlorobenzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,methyl 2-(benzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,2-[(2-methyl-2-propenyl)sulfanyl]-4,5-dihydro-1,3-thiazole,2-[benzylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[(2-methylpropyl)sulfanyl]-4,5-dihydro-1,3-thiazole,2-[allylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[4-nitrophenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[4-methoxyphenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[4-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[2-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[3-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)-1-phenylethanone,2-[methylsulfanyl]-4,5-dihydro-1,3-thiazole,2-{[(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)methyl]sulfanyl}-4,5-dihydro-1,3-thiazole, 2-[phenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[(4-tert-butylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine2-[(4-chloro-2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine2-[(pentachlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine2-[(2,4,6-trichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine, and2-[(2,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine.
 6. Aprocess for preparing a compound of the formula (I)

wherein R¹ represents hydrogen or in each case optionally substitutedalkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl, R² representshydrogen, alkoxycarbonyl or alkylcarbonyl and n represents 1 or 2,except for 2-(phenylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,2-[(3-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(4-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-(methylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,2-[(4-methoxyphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(4-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-(ethylsulfanyl)-5,6-dihydro-4H-1,3-thiazine,2-[(4-nitrophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(3,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(2-chlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-1-phenylethanone,2-{[3-(trifluoromethyl)-1,2,4-thiadiazol-5-yl]sulfanyl}-5,6-dihydro-4H-1,3-thiazine,2-[(2,4-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(4-bromophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(2,6-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(3,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(3-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,2-[(2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine,4-(5,6-dihydro-4H-1,3-thiazin-2-ylsulfanyl)-N,N-dimethylaniline,2-[(4-fluorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine, methyl2-(methylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate, methyl2-(4-chlorobenzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,methyl 2-(benzylsulfanyl)-4,5-dihydro-1,3-thiazole-4-carboxylate,2-[(2-methyl-2-propenyl)sulfanyl]-4,5-dihydro-1,3-thiazole,2-[benzylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[(2-methylpropyl)sulfanyl]-4,5-dihydro-1,3-thiazole,2-[allylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[4-nitrophenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[4-methoxyphenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[4-chlorophenysulfanyl]-4,5-dihydro-1,3-thiazole,2-[2-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[3-chlorophenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)-1-phenylethanone,2-[methylsulfanyl]4,5-dihydro-1,3-thiazole,2-{[(4,5-dihydro-1,3-thiazol-2-ylsulfanyl)methyl]sulfanyl}-4,5-dihydro-1,3-thiazole, 2-[phenylsulfanyl]-4,5-dihydro-1,3-thiazole,2-[(4-tert-butylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine2-[(4-chloro-2-methylphenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine2-[(pentachlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine2-[(2,4,6-trichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine2-[(2,5-dichlorophenyl)sulfanyl]-5,6-dihydro-4H-1,3-thiazine, whereinthe process comprises reacting: (1) mercaptans of the formula (II) orsalts thereof R¹—SH  (II) wherein R¹ represents hydrogen or in each caseoptionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aryl orheterocyclyl, with (2) isothiocyanates of the general formula (IV)

wherein R² represents hydrogen, alkoxycarbonyl or alkylcarbonyl and n is1 or 2, and X represents halogen or a leaving group,
 7. The processaccording to claim 6, wherein the process is carried out in the presenceof a diluent or in the presence of an acid binder, or both in thepresence of a diluent and an acid binder.
 8. A method for protecting anindustrial material against attack and/or destruction by anmicroorganisms, characterized in that at least one compound of theformula (I) according to claim 1 comprising (a) placing a compound offormula (I) on the organism or the habitat of the organism, and (b)allowing the compound of formula (I) to act on the microorganism or itshabitat.
 9. A microbicidal composition for protecting industrialmaterials, comprising at least one compound of a compound of the formula(I)

wherein R¹represents hydrogen or in each case optionally substitutedalkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl, R² representshydrogen, alkoxycarbonyl or alkylcarbonyl and n represents 1 or 2, andat least one solvent or diluent.
 10. The composition of claim 9, whereinthe composition further comprises a processing auxiliary and anadditional antimicrobially active substance component.
 11. Thecompositions according to claim 10, wherein the additionalantimicrobially active substance component is selected from the groupconsisting of fungicides, bactericides, acaricides, nematicides,algicides, insecticides, and combinations thereof.
 12. An industrialmaterial comprising an industrial material with a compound of theformula (I)

wherein R¹ represents hydrogen or in each case optionally substitutedalkyl, alkenyl, alkinyl, cycloalkyl, aryl or heterocyclyl, R² representshydrogen, alkoxycarbonyl or alkylcarbonyl and n represents 1 or 2.